JP2000204130A - Photo-sensitive paste and production of display material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject photo-sensitive paste that can attain pattern processing of high aspect ratio and high definition in low costs and is useful in the plasma display or the like by admixing a specific photo-sensitive polymer to a photo-sensitive organic component. SOLUTION: This paste comprises (A) inorganic fine particles and (B) photo- sensitive organic components in which the component B includes a photo-sensitive polymer prepared by ring-opening polyaddition reaction of (i) an unsaturated group-bearing alicyclic epoxy compound to (ii) a carboxyl group-bearing copolymer. In a preferred embodiment, the component B is a compound of the formula (R is H or methyl), the component (i) is a copolymer of (meth)acrylate ester(s) and (meth)acrylic acid(s) and the weight ratio of the component A to the component B is (5-50 wt.%)/(95-50 wt.%). The component (A) has the glass transition point of 430-500 deg.C and the softening point of 470-580 deg.C and includes a glass powder containing lithium oxide with the average particle size of 2-3.5 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive paste and a method for manufacturing a display using the same, and for manufacturing various displays including a plasma display, a plasma addressed liquid crystal display, a field emission display, and a circuit material. It is used for pattern processing such as.

[0002]

2. Description of the Related Art In recent years, miniaturization and high definition of displays have been advanced, and accordingly, improvement of pattern processing technology has been desired. In particular, a material capable of patterning an inorganic material such as glass with high accuracy and a high aspect ratio is desired for forming a partition of a plasma display panel.

Conventionally, when patterning an inorganic material, screen printing using a paste composed of an inorganic powder and an organic binder is often used. However, screen printing has a drawback that a highly accurate pattern cannot be formed.

As a method for solving this problem, Japanese Patent Laid-Open No.
JP-A-296534, JP-A-2-165538 and JP-A-5-34292 propose a method of forming a photosensitive paste by using a photolithography technique. However, since the sensitivity of the photosensitive paste and the resolution of pattern formation are low, a partition wall with a high aspect ratio and high definition could not be obtained. For example, when processing a pattern with a thickness exceeding 80 μm, multiple processing (screen printing / exposure / development) is required.
There was a disadvantage that the process became long.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photosensitive paste which enables low-cost pattern processing with a high aspect ratio and high definition.

[0006]

The object of the present invention is achieved by the following constitution.

In a photosensitive paste comprising inorganic fine particles and a photosensitive organic component, the photosensitive organic component is obtained by ring-opening addition of an unsaturated group-containing alicyclic epoxy compound to a carboxyl group-containing copolymer. And a method for producing a display member using the same.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The photosensitive paste of the present invention contains a photosensitive polymer obtained by ring-opening addition of an unsaturated group-containing alicyclic epoxy compound to a carboxyl group-containing copolymer.

[0009] The carboxyl group-containing copolymer is (meth)
It is obtained by copolymerization of acrylic acid and (meth) acrylate.

Examples of (meth) acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-
Butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate,
Benzyl acrylate, butoxyethyl acrylate,
Butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate, 2-hydroxy Propyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate,
Stearyl acrylate, trifluoroethyl acrylate, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, benzyl mercaptan acrylate, and hydrogen atoms of these aromatic rings Examples thereof include monomers in which 1 to 5 carbon atoms are substituted with chlorine or bromine atoms, and compounds in which the acrylate in the molecule of the above compound is changed to methacrylate.

Further, the copolymer may contain a copolymer component other than (meth) acrylic acid and (meth) acrylate. For example, unsaturated carboxylic acids such as itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, or anhydrides thereof, or styrene, p-methylstyrene, o-methylstyrene, m
-Methyl styrene, chlorinated styrene, brominated styrene,
Unsaturated compounds other than unsaturated carboxylic acids such as α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole and acrylonitrile. And saturated compounds.

A method for producing a copolymer comprising these unsaturated compounds can be obtained, for example, by performing solution polymerization using a general-purpose polymerization initiator such as 2,2'-azobisisobutyronitrile.

In the present invention, as the carboxyl group-containing copolymer, a copolymer comprising an acrylic ester or a methacrylic acid ester and acrylic acid or methacrylic acid is most preferred.

As the unsaturated group-containing alicyclic epoxy compound, 3,4-epoxycyclohexylmethyl methacrylate or 3,4-epoxycyclohexylmethyl acrylate represented by the following formula (1) or a caprolactone-modified product thereof is used. Preferably, among others, the following formula (2)
3,4-epoxycyclohexylmethyl methacrylate represented by the following formula is most preferred.

[0015]

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[0016]

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The photosensitive polymer used in the photosensitive paste of the present invention is obtained by ring-opening addition of the unsaturated group-containing alicyclic epoxy compound to the carboxyl group-containing copolymer. In the ring-opening addition reaction, the ratio of the unsaturated group-containing alicyclic epoxy compound to be reacted with the carboxyl group-containing copolymer is such that the amount of double bonds per 1 kg of the resin after the addition reaction is 1.
0 to 3.5 mol, 286 to 1 in terms of double bond equivalent
It is preferable to set to be 000 g / mol. The amount of double bonds contained in 1 kg of the resin after the reaction was determined as follows.
By setting it to 0 mol or more, sufficient curability can be obtained. When the content is 3.5 mol or less, sufficient storage stability can be obtained.

The weight average molecular weight of the thus obtained photosensitive polymer is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, sufficient form retention can be obtained, and when the weight average molecular weight is 100,000 or less, development can be easily performed.

The acid value is 25 to 200 mg KOH / g.
And more preferably 50 to 150.
mg KOH / g. By setting the acid value to 25 mgKOH / g or more, the removability of unnecessary portions becomes good during development, and by setting the acid value to 200 mgKOH / g or less, it is possible to sufficiently obtain a contrast between a cured portion and an uncured portion during development. it can.

In the photosensitive paste of the present invention, the photosensitive organic component means a portion excluding the inorganic fine particles, that is, the whole photosensitive organic component. Photosensitive organic components include
In addition to the above photosensitive polymer, a photosensitive monomer, a photosensitive oligomer, a photosensitive polymer other than the above polymer, a photopolymerization initiator, a light absorber, a sensitizer, a sensitization aid, a polymerization inhibitor,
Binder, plasticizer, thickener, organic solvent, antioxidant,
Additive components such as dispersants, organic or inorganic suspending agents and leveling agents can be added. The photosensitive paste of the present invention comprises 95 to 50% by weight of inorganic fine particles and 5 to 5% by weight.
It preferably comprises 0% by weight of a photosensitive organic component.

Examples of the photosensitive monomer include compounds having a carbon-carbon unsaturated bond as described below. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxy Triethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-
Ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene Glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-
Butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate,
Methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1 -Naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, diacrylate of bisphenol A-propylene oxide adduct, thiophenol acrylate, benzyl mercaptan acrylate, and aromatic rings thereof Of the hydrogen atoms
A monomer in which five are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene , Brominated α-methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole and those in which acrylate in the molecule is partially or entirely changed to methacrylate, γ
-Methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone and the like. These monomers can be used alone or in combination of two or more.

An oligomer or polymer obtained by polymerizing at least one of these photosensitive monomers can also be used. Furthermore, by adding an unsaturated acid such as an unsaturated carboxylic acid and copolymerizing, the developability after exposure can be improved. Although this oligomer or polymer can be used as a binder as it is, it can be used as a photosensitive polymer or photosensitive oligomer having photosensitivity by adding a photoreactive group to a side chain or a molecular terminal. Can also. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group. The method of adding such a side chain to an oligomer or a polymer includes an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, a mercapto group, an amino group, a hydroxyl group, and a carboxyl group in the polymer, acrylic acid chloride, and methacrylic acid. There is a method of making an acid chloride or allyl chloride by an addition reaction. Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl ether crotonate, and glycidyl ether isocrotonic acid. As the ethylenically unsaturated compound having an isocyanate group,
(Meth) acryloyl isocyanate, (meth) acryloylethyl isocyanate and the like. Further, ethylenically unsaturated compounds having a glycidyl group or an isocyanate group and acrylic acid chloride, methacrylic acid chloride or allyl chloride is a mercapto group in the polymer,
0.05 to amino group, hydroxyl group and carboxyl group
It is preferable to add one molar equivalent.

Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, -Benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-
2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether Benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p- (Azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-buta On-2- (o-methoxycarbonyl) oxime, 1-phenyl - propane-2-
(O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2 -Methyl- [4- (methylthio) phenyl]
-2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N
-Phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone,
Examples include a combination of a photoreducing dye such as benzoin peroxide and eosin or methylene blue with a reducing agent such as ascorbic acid or triethanolamine. These can be used alone or in combination of two or more. The photopolymerization initiator is 0.05 to 10% by weight based on the organic component.
And more preferably 0.1 to 10% by weight. By setting the amount of the photopolymerization initiator to 0.05% by weight or more, the exposure sensitivity is improved, and by setting the amount of the photopolymerization initiator to 10% by weight or less, the residual ratio of the exposed portion is reduced. Can be prevented.

It is also effective to add a light absorber. By adding a compound having a high effect of absorbing ultraviolet light or visible light, a high aspect ratio, high definition, and high resolution can be obtained.

As the light absorber, those comprising an organic dye are preferably used. Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, anthraquinone dyes, benzophenone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes and the like can be used. . The organic dye is preferable because it does not remain in the insulating film after firing even when added as a light absorber, so that the deterioration of the insulating film characteristics due to the light absorber can be reduced. Among these,
Azo and benzophenone dyes are preferred.

The addition amount of the organic dye is preferably 0.05 to 5 parts by weight. When the content is 0.05% by weight or more, a sufficient effect of absorbing scattered light can be obtained, and when the content is 5% by weight or less, it is possible to prevent the insulating film characteristics after firing from being deteriorated.

A sensitizer can be added for the purpose of improving the sensitivity. As the sensitizer, for example, 2,4
-Diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal ) -4-Methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone,
4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonaphthothiazole, 1,3-
Bis (4-dimethylaminobenzal) acetone, 1,3
-Carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N- Examples include phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. These are one or two
A mixture of more than one species can be used. Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is added to the photosensitive paste of the present invention, the amount is usually 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the organic component. By setting the amount of the sensitizer to 0.05% by weight or more, the exposure sensitivity can be improved, and by setting the amount of the sensitizer to 10% by weight or less, the residual ratio of the exposed portion becomes too small. Can be prevented.

In the present invention, it is also effective to add an antioxidant. The antioxidant has a radical chain inhibiting action, a triplet eliminating action, and a hydroperoxide decomposing action.

Since the photosensitive paste contains a large amount of inorganic fine particles in a dispersed state, light scattering inside the paste due to exposure light is inevitable. ) Is easy to occur. The walls of the pattern are desirably vertically cut and rectangular. Ideally, it is dissolved in the developer below a certain exposure amount, and insoluble in the developer above it. In other words, it is preferable that even if a small amount of light is exposed to the scattered light, it is not dissolved in a developing solution and the pattern shape is not thickened or buried between patterns.

When an antioxidant is added to the photosensitive paste, extra light reactions due to scattered light are suppressed by capturing radicals or returning the excited photopolymerization initiator or sensitizer to the ground state. Is done. Therefore, a photoreaction occurs rapidly at an exposure amount that cannot be suppressed by the antioxidant,
The contrast between dissolution and insolubility in the developer can be increased.

Specifically, p-benzoquinone, naphthoquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, hydroquinone , Pt-butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5
-Di-t-amylhydroquinone, di-t-butyl-p-
Cresol, hydroquinone monomethyl ether, α-naphthol, hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene Nitrobenzene,
Picric acid, quinone dioxime, cyclohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone, (2,2 ′
-Thiobis (4-t-octylphenolate) -2-ethylhexylaminonickel- (II), 4,4'-thiobis- (3-methyl-6-t-butylphenol),
2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-thiobis- (4-methyl-
6-t-butylphenol), triethylene glycol-bis [3- (t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [(3,5-di-t- Butyl-4-hydroxyphenyl) propionate], 1,2,3-trihydroxybenzene, and the like, but are not limited thereto. In the present invention, one or more of these can be used.

The amount of the antioxidant added is 0.1 to 30% by weight, more preferably 0.5 to 20% by weight in the photosensitive paste.
% By weight. By making it 0.1% by weight or more,
The contrast of dissolution and insolubility in the developer can be increased, and by setting the content to 30% by weight or less, the sensitivity of the photosensitive paste is not reduced, so that a large amount of exposure is required and the polymerization degree is low. There is no possibility that the pattern shape cannot be maintained due to the rise.

To adjust the viscosity of the solution, an organic solvent may be added to the photosensitive paste of the present invention. As the organic solvent used at this time, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, N-methyl Pyrrolidone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and an organic solvent mixture containing at least one of these are used.

The inorganic fine particles in the present invention are glass powder, metal powder, ceramic fine particles and the like, and particularly useful when glass powder or metal powder is used.

As the glass powder, the glass transition point 430
When the paste contains glass powder having a softening point of 500 ° C. and a softening point of 470-580 ° C. in an amount of 50% by weight or more, pattern processing can be performed on a substrate used for a normal display.

By using a glass powder having such a glass transition point and softening point and blending a metal oxide so that the refractive index of the glass powder is 1.5 to 1.65, the glass High-precision pattern processing becomes possible by matching the refractive index of the powder with the photosensitive organic component and suppressing light scattering. For example, silicon oxide: 22, aluminum oxide: 23, boron oxide: 33, lithium oxide: 9,
A glass powder composed of magnesium oxide: 7, barium oxide: 4 and zinc oxide: 2 (% by weight) has a glass transition point of 490 ° C., a softening point of 528 ° C., and a g-line wavelength (4%).
The refractive index at 36 nm) is 1.59, and can be preferably used as the inorganic fine particles of the invention.

As the inorganic fine particles used in the photosensitive paste of the present invention, for example, a glass powder containing the following composition can be preferably used.

Lithium oxide: 3 to 10% by weight Silicon oxide: 10 to 30% by weight Boron oxide: 20 to 40% by weight Barium oxide: 2 to 15% by weight Aluminum oxide: 10 to 25% by weight Among these, lithium oxide Is particularly useful. By using a glass powder containing 3 to 10% by weight of lithium oxide, not only the control of the thermal softening temperature and the coefficient of thermal expansion becomes easy, but also the average refractive index of the glass is lowered. Therefore, it is easy to reduce the difference in the refractive index from the organic component. The addition amount of the alkali metal oxide is preferably 10% by weight or less, more preferably 8% by weight or less, in order to improve the stability of the paste.

The silicon oxide is preferably blended in a range of 10 to 30% by weight, and if it is 10% by weight or more, the glass layer can have denseness, strength and stability, and can have a coefficient of thermal expansion of a desired value. Since it can be within the range, no mismatch with the glass substrate occurs. Further, when the content is 30% by weight or less, there is an advantage that the softening point is lowered, and baking on a glass substrate becomes possible.

It is preferable that boron oxide is blended in the range of 20 to 40% by weight. When the content is 40% by weight or less, the stability of the glass can be maintained. Boron oxide dissolves glass powder at a temperature of about 800 to 1200 ° C., and impairs electrical, mechanical and thermal properties such as electrical insulation, strength, coefficient of thermal expansion, and denseness of an insulating layer even when silicon oxide is large. Baking temperature 540-61 to prevent
It is blended to control the temperature within the range of 0 ° C. If it is less than 20% by weight, the strength of the insulating layer is reduced, and the stability of the glass is reduced.

Barium oxide is preferably blended in the range of 2 to 15% by weight. When the content is 2% by weight or more, it is easy to control the glass baking temperature and the electrical insulation. Further, when the content is 15% by weight or less, stability and denseness of the glass layer can be maintained.

It is preferable that aluminum oxide is blended in the range of 10 to 25% by weight. Aluminum oxide is added to increase the strain point of the glass. When the content is 10% by weight or more, the strength of the glass layer is improved. By setting the content to 25% by weight or less, the glass can be easily baked on a glass substrate without the heat-resistant temperature of the glass becoming too high, and a dense insulating layer can be obtained at a temperature of 600 ° C. or less. .

In the glass powder, the content of sodium oxide, potassium oxide, yttrium oxide, etc., which deteriorates the discharge characteristics of the plasma, is preferably 5% by weight or less, and more preferably no such content.

The glass powder may contain titanium oxide, zirconium oxide, etc.
Preferably, it is less than about 10% by weight. Zirconium oxide is effective in controlling the softening point, transition point and electrical insulation of glass.

As a method for producing a glass powder, for example, raw materials such as lithium oxide, silicon oxide, boron oxide, barium oxide, and aluminum oxide are mixed so as to have a predetermined composition and melted at 900 to 1200 ° C. It is quenched, made into a glass frit, and then crushed to a fine powder of 1 to 5 μm. As a raw material, a high-purity carbonate, oxide, hydroxide, or the like can be used. Also, depending on the type and composition of the glass powder, the use of a powder prepared uniformly by a sol-gel method using an ultra-high purity alkoxide or organometallic material of 99.99% or more will result in a high electrical resistance and a high density. It is preferable because a high-strength insulating layer having few pores can be obtained.

The particle diameter of the glass powder used in the above is selected in consideration of the shape of the pattern to be produced, and the powder has a particle diameter of 50% by weight (average particle diameter) of 2 to 2.
It is preferable that the thickness is 3.5 μm and the top size is 15 μm or less. Furthermore, a 10% by weight particle size is 0.6 to 1.5 μm.
m, 90% by weight particle size 4-8 μm, specific surface area 1.5-
It is preferred to have 2.5 m ² / g. More preferably, the average particle size is 2.5 to 3.5 μm, and the specific surface area is 1.7.
２2.4 m ² / g. Within this range, light is sufficiently transmitted at the time of exposure to ultraviolet light, and a partition pattern with a small line width difference between the upper and lower portions can be obtained. Further, by setting the average particle diameter to 2.0 μm or more and the specific surface area to 2.5 m ² / g or less, the powder does not become too fine, and it is possible to prevent light from being scattered at the time of exposure and hardening an unexposed portion. .

In the case of the electrode paste, a conductive metal powder is used as the inorganic fine particles. As metal powder,
Metals such as gold, nickel, silver, palladium and platinum or alloys containing these are preferably used, but those containing 90 to 100% by weight of silver are particularly preferable. By setting the silver content to 90% by weight or more, the sinterability can be improved and the resistance value can be reduced.

It is preferable to control the average particle size of the metal powder used in the above to 0.5 to 5 μm. By setting the average particle diameter to 0.5 μm or more, it is possible to suppress the aggregation of the metal powder and obtain a paste in a state where the powder is highly dispersed. Further, by setting the average particle diameter to 5 μm or less, the surface of the paste molded body does not become rough, and there is no concern that pinholes or disconnections occur when a thin electrode layer is formed.

Further, it is preferable that the electrode paste is mixed with glass powder for the purpose of improving the adhesion to the glass substrate. As an example of the glass powder used here, a glass powder having a total content of bismuth oxide and lead oxide of 30 to 90% by weight is preferable. When the content of these components in the glass powder decreases, the melting temperature increases, and the adhesive strength to the glass substrate decreases. When the content is excessive, the content tends to be easily deteriorated by moisture.

The photosensitive paste is usually made of an ultraviolet absorber,
Antioxidants, inorganic fine particles, photosensitive organic components, organic dyes,
Various components such as a dispersant, a light absorbing agent, and a solvent are blended so as to have a predetermined composition, and then uniformly mixed and dispersed with a three-roller or a kneader to produce.

The viscosity of the paste is appropriately adjusted by the addition ratio of inorganic fine particles, a thickener, an organic solvent, a plasticizer, an anti-settling agent, etc., but the range is from 2000 to 200,000 cp.
s (centipoise). For example, when the coating on the substrate is performed by the spin coating method, 20
00 to 5000 cps is preferable. In order to obtain a film thickness of 10 to 20 μm by applying once by the screen printing method, 50,000 to 2
100,000 cps is preferred. When using a blade coater method, a die coater method, or the like, 10,000 to 50,000 cps is preferable.

Next, an example of performing pattern processing using a photosensitive paste will be described, but the present invention is not limited to this.

On the substrate, the photosensitive paste is applied entirely or partially. As a coating method, a method such as a screen printing method, a bar coater, a roll coater, a die coater, or a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and the viscosity of the paste.

The glass substrate used in the present invention is not particularly limited, but may be a general soda-lime glass, a glass obtained by annealing a soda-lime glass, a high strain point glass (trade name: PD-200, manufactured by Asahi Glass Co., Ltd.), or the like. Can be used. There is no particular limitation on the size of the glass substrate,
Glass with a thickness of 1-5 mm can be used.

Here, when applying the paste on the substrate,
Surface treatment of the substrate can be performed to enhance the adhesion between the substrate and the coating film. Examples of the surface treatment liquid include silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacrylic acid). Roxypropyl) trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like, or an organic metal such as , Organic titanium,
Organic aluminum, organic zirconium and the like. A silane coupling agent or an organic metal diluted with an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol to a concentration of 0.1 to 5% is used. Used.
Next, this surface treatment liquid is uniformly applied on a substrate by a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes to perform surface treatment.

After application, exposure is performed using an exposure device. As an exposure apparatus, a proximity exposure machine or the like can be used. Also, when performing large area exposure,
After applying the photosensitive paste on the substrate, by performing exposure while transporting, with an exposure machine with a small exposure area,
A large area can be exposed.

After the exposure, development is carried out using the difference in solubility between the exposed part and the unexposed part in the developing solution.
It is performed by a dipping method, a spray method, or a brush method. An organic solvent in which an organic component in the photosensitive paste can be dissolved is used as the developer. In addition, water may be added to the organic solvent as long as its solubility is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an aqueous alkali solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution and the like can be used, but it is preferable to use an organic alkaline aqueous solution since an alkaline component can be easily removed during firing.

As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like.

The concentration of the aqueous alkali solution is usually 0.05 to 5
%, More preferably 0.1 to 1% by weight. If the alkali concentration is too low, it is difficult to remove the soluble portion, and if the alkali concentration is too high, the pattern tends to peel off or corrode the non-soluble portion. The development temperature during development is preferably from 20 to 50 ° C. from the viewpoint of process control.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste or substrate, but firing is performed in an atmosphere such as air, nitrogen, or hydrogen. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

The firing temperature is 400 to 1000 ° C. When processing a pattern on a glass substrate, 480 to 610
The firing is carried out at a temperature of 10 ° C. for 10 to 60 minutes.

[0062]

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to this. The concentration (%) in the examples and comparative examples is% by weight. Example 1 A mixture having the following composition was kneaded with three rollers. 1) 60 parts by weight of glass powder 2) 10 parts by weight of polymer ("Cyclomer P" ACA250 manufactured by Daicel Chemical Industries, Ltd.) 3) 10 parts by weight of monomer (trimethylolpropane triacrylate) 4) photopolymerization initiator (2- Benzyl-2-dimethylamino-1- (morpholinophenyl) butanone-1) 3 parts by weight 5) Organic dye (Sudan IV) 0.01 parts by weight 6) Solvent (γ-butyrolactone) 17 parts by weight As the above glass powder Has a composition of Li ₂ O: 9%, S
iO ₂ : 22%, Al ₂ O ₃ : 23%, B ₂ O ₃ : 33%,
BaO: 4%, ZnO: 2%, MgO: 7% were used. This glass powder has an average refractive index of 1.586, a glass transition point and a softening point of 476 ° C. and 519 ° C., respectively, and an average particle size of 2.6 μm.

Further, a polymer (Daicel Chemical Industries, Ltd.)
"Cyclomer P" ACA250) is a photosensitive polymer obtained by ring-opening addition of 3,4-epoxycyclohexylmethyl acrylate to a carboxyl group-containing copolymer having methacrylic acid and butyl acrylate as copolymer components. Weight average molecular weight is 10,000, acid value is 70 mg KO
H / g.

The obtained paste was uniformly applied on a soda glass substrate by using a screen printing method. Coating and drying were repeated several times or more in order to avoid pinholes or the like on the coating film, and coating was performed so that the dry thickness became 180 μm. The drying in the middle was performed at 80 ° C. for 10 minutes, and finally at 80 ° C. for 60 minutes.

Next, exposure was carried out via a photomask for forming a partition pattern for a plasma display (striped pattern, pattern pitch 130 μm, line width 30 μm). At this time, to prevent the mask from being contaminated,
A gap of 50 μm was provided between the mask and the coating surface. Thereafter, development was performed by applying a 0.3% by weight aqueous solution of monoethanolamine kept at 35 ° C. in a shower for 150 seconds to form a stripe-shaped partition pattern on the substrate.

Subsequently, the partition pattern was observed with a microscope.
The optimum exposure dose at which exfoliation of the exposed portion, meandering of the pattern and burying between patterns (remaining film) did not occur was examined. 150
With the exposure amount of mJ / cm ² , a good partition pattern was formed without peeling of the exposed portion, meandering of the pattern and burying between the patterns.

After the pattern processing is completed, the substrate is kept at 80 ° C. for 15 minutes.
After drying for minutes, baking was performed at 570 ° C. for 15 minutes to form partition walls. Example 2 A partition pattern was formed in the same manner as in Example 1 except that the composition was changed as follows. 1) Glass powder 55 parts by weight 2) Polymer 10 parts by weight 3) Monomer 1 (trimethylolpropane triacrylate) 9 parts by weight 4) Monomer 2 (2-hydroxyethyl methacrylate) 6 parts by weight 5) Photopolymerization initiator (2- Benzyl-2-dimethylamino-1- (morpholinophenyl) butanone-1) 3 parts by weight 6) Organic dye (Basic Blue 26) 0.01 part by weight 7) Solvent (dipropylene glycol monomethyl ether) 17 parts by weight Polymer Are carboxyl group-containing copolymers containing methacrylic acid and butyl acrylate as copolymer components,
-A photosensitive polymer obtained by ring-opening addition of epoxycyclohexylmethyl acrylate was used. The weight average molecular weight is 18
000, and the acid value was 111 mgKOH / g.

In the same manner as in Example 1, the partition pattern was observed with a microscope, and the optimum exposure amount at which exfoliation of the exposed portion, meandering of the pattern, and burying between patterns (remaining film) did not occur was examined. At an exposure amount of 200 mJ / cm ² , the exposed portion peels off,
A good partition pattern was formed without meandering of the pattern and no burial between the patterns. Example 3 A partition pattern was formed in the same manner as in Example 1 except that the polymer was changed as follows.

The polymer used here is a photosensitive polymer obtained by ring-opening addition of 3,4-epoxycyclohexylmethyl methacrylate to a carboxyl group-containing copolymer having methyl methacrylate and methacrylic acid as copolymer components. Weight average molecular weight: 20,000, acid value: 120 mg
KOH / g.

Exposure and development were performed in the same manner as in Example 1 to form a partition pattern. With an exposure amount of 120 mJ / cm ² , there is no peeling of exposed portions, meandering of patterns and burying between patterns, and no shaving of pattern edges.
A good partition pattern was formed. Example 4 A mixture having the following composition was kneaded with three rollers. 1) 60 parts by weight of silver powder (average particle size 1.5 μm) 2) 10 parts by weight of polymer (“Cyclomer P ACA250” manufactured by Daicel Chemical Industries, Ltd.) 3) 10 parts by weight of monomer (trimethylolpropane triacrylate) 4 ) Photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one) 3 parts by weight 5) Glass powder (bismuth borosilicate glass) 2 parts by weight 6) Solvent (Γ-butyrolactone) 15 parts by weight The obtained paste was uniformly applied on a soda glass substrate by using a screen printing method. Coating and drying were repeated several times or more in order to avoid the occurrence of pinholes and the like on the coating film, so that the coating thickness was 6 μm. The drying in the middle was performed at 80 ° C. for 10 minutes, and finally at 80 ° C. for 60 minutes.

Next, a photomask for forming an electrode pattern for a plasma display (pattern pitch 140 μm,
Exposure was performed through a line width of 50 μm. At this time, in order to prevent the mask from being contaminated, 50 μm
m gap was provided. Then, a 0.3% by weight aqueous solution of monoethanolamine kept at 30 ° C.
The development was performed by spending 0 seconds to form an electrode pattern on the substrate.

With respect to the obtained electrode pattern, the presence or absence of pinholes, peeling, and disconnection was examined to determine the optimum exposure. 1
At a light exposure of 00 mJ / cm ² , a good electrode pattern as in the mask without pinholes, peeling or disconnection was obtained.

After the pattern processing is completed, the substrate is kept at 80 ° C. for 15 minutes.
After drying for minutes, firing was performed at 590 ° C. for 15 minutes to form an electrode. Example 5 An electrode pattern was formed in the same manner as in Example 4 except that the photosensitive polymer used in Example 3 was changed to the photosensitive polymer used in Example 3.

Exposure and development were performed in the same manner as in Example 4 to form an electrode pattern. With an exposure of 80 mJ / cm ² ,
A good electrode pattern without pinholes, peeling, disconnection and edge floating was obtained. Comparative Example 1 A partition wall pattern was formed in the same manner as in Example 1 except that a methacrylic acid / methyl methacrylate (15/85) copolymer was used instead of the polymer of Example 1. The pattern of the partition walls after development was remarkably meandering, and was not resolved even when the exposure amount and the development time were changed, and a good pattern was not obtained. Comparative Example 2 An electrode pattern was formed in the same manner as in Example 3 except that a methacrylic acid / methyl methacrylate copolymer (15/85) was used instead of the polymer of Example 3. 500
Even after exposure to J / cm ² , peeling occurred during development.

[0075]

According to the method for producing a photosensitive paste and a member for a display of the present invention, pattern processing of a thick film can be performed with a low exposure amount and in a short time. This makes it possible to improve the definition of a thick film such as a display member or a circuit material, high-precision pattern processing, and simplify the process. The method for producing a photosensitive paste and a member for a display of the present invention is particularly effective for forming a partition wall and an electrode of a plasma display member with high precision.

Claims (13)

[Claims] 1. A photosensitive paste comprising inorganic fine particles and a photosensitive organic component, wherein the photosensitive organic component is obtained by ring-opening addition of an unsaturated group-containing alicyclic epoxy compound to a carboxyl group-containing copolymer. A photosensitive paste comprising a hydrophilic polymer. 2. The photosensitive paste according to claim 1, wherein the unsaturated group-containing alicyclic epoxy compound is an unsaturated group-containing alicyclic epoxy compound represented by the following general formula (1). Embedded image (Here, R represents a hydrogen atom or a methyl group.) 3. The photosensitive paste according to claim 1, wherein the unsaturated group-containing alicyclic epoxy compound is an unsaturated group-containing alicyclic epoxy compound represented by the following formula (2). Embedded image 4. The carboxyl group-containing copolymer is a copolymer comprising an acrylate or methacrylate and acrylic acid or methacrylic acid.
The photosensitive paste as described in the above. 5. The photosensitive paste according to claim 1, wherein the photosensitive paste comprises 95 to 50% by weight of inorganic fine particles and 5 to 50% by weight of a photosensitive organic component. 6. The photosensitive paste according to claim 1, wherein the inorganic fine particles include glass powder. 7. The glass powder has a glass transition point of 430 to 50.
7. The photosensitive paste according to claim 6, which is a glass powder containing lithium oxide having a temperature of 0 ° C. and a softening point of 470 to 580 ° C. and an average particle diameter of 2 to 3.5 μm. 8. The photosensitive paste according to claim 1, wherein the inorganic fine particles contain a conductive metal powder. 9. The photosensitive paste according to claim 8, wherein the conductive metal powder is a conductive metal powder containing 90 to 100% by weight of silver and having an average particle diameter of 0.5 to 5 μm. 10. A method for manufacturing a member for a display, comprising applying the photosensitive paste according to claim 1 on a substrate, forming a pattern through exposure and development, and further firing. 11. A method for manufacturing a member for a display, comprising applying the photosensitive paste according to claim 6 on a substrate, forming a pattern through exposure and development, and further baking to form a partition. . 12. A method for manufacturing a member for a display, comprising applying the photosensitive paste according to claim 8 on a substrate, forming a pattern through exposure and development, and further baking to form an electrode. . 13. The method for manufacturing a display member according to claim 10, wherein the display member is a plasma display member.